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Novel fluorine-containing cyclic polymer

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US4897457A
US4897457A US07233820 US23382088A US4897457A US 4897457 A US4897457 A US 4897457A US 07233820 US07233820 US 07233820 US 23382088 A US23382088 A US 23382088A US 4897457 A US4897457 A US 4897457A
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polymer
polymerization
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Masaru Nakamura
Isamu Kaneko
Kazuya Oharu
Gen Kojima
Masashi Matsuo
Shunichi Samejima
Motoi Kamba
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Asahi Glass Co Ltd
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Asahi Glass Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F16/00Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F16/12Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F16/32Monomers containing two or more unsaturated aliphatic radicals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/44Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26 - B01D71/42

Abstract

A fluorine-containing thermoplastic resinous polymer which consist essentially of a group (a) of repeating units of a cyclic structure to be represented by the following general formula: ##STR1## (where: n is an integer of 1 to 2); the polymer having a molecular weight such that the intrinsic viscosity thereof may become at least 0.1.
A fluorine-containing thermoplastic resinous polymer which consists essentially of:
(i) a group (a) of repeating units to be represented by the following general formula: ##STR2## (where: n is an integer of 1 or 2), and (ii) a group (b) of repeating units to be represented by the following general formula:
--CF.sub.2 --CFX)--
(where: X is selected from fluorine, chlorine. O--CF2 CF2 CF3, O--CF2 CF(CF3)OCF2 CF2 SO2 F, and O--CF2 CF2 CF2 COOCH3)
the polymer containing therein at least 80% by weight of the group of repeating units (a), and having a molecular weight such that the intrinsic viscosity thereof may be become at least 0.1.

Description

This invention relates to a novel fluorine-containing cyclic polymer, and, more particularly, it is concerned with a thermoplastic resinous fluorine-containing cyclic polymer having a particular asymmetrical cyclic structure in the main chain thereof.

With regard to the cyclic polymerization of hydrocarbon-type monomers, there have been done various researches, and a multitude of reports have been known in general, inclusive of three-membered cyclic polyether to large-membered cyclic polyether.

On the other hand, there have been known various fluorine-containing polymers, of which polytetrafluoroethylene and many others are already practically put into industrial use.

However, most of these fluorine-containing polymers contain therein the main chain in straight form based on vinyl monomer such as fluoro-olefin, (meth)acrylate having the fluoro-alkyl group in its side chain, etc.

There is very few example of polymer to be obtained by cyclic polymerization of a fluorine-type monomer, and it has only been known that a compound of a general formula: CF2 ═CF(CF2)x CF═CF2 (where: x is an integer of from 1 to 3) undergoes the cyclic polymerization by the γ-rays (vide: L. A. Waal, Fluoropolymer, Wiley-Science, 4, High Pressure Polymerization, p 127). It has also been known that a compound represented by the following general formula: CF2 ═CF--CF2 --CFCl--CF2 CF═CF2 is polymerized to yield a transparent and highly elastic film which is excellent in its heat-resistance and oxidation-resistance (vide: D. S. Ballantine et at., U.S. Atomic Energy Commission, BNL-296 (T-50) 18, 1954). However, all these polymers do not contain the ether bond in its principal chain, on account of which they can not be said to be necessarily satisfactory in their transparency and flexibility.

Moreover, British patent specification No. 1,106,344, U.S. Pat. No. 3,418,302, and others described fluorine-containing cyclic polymers which contain in the main chain thereof a cyclic structure having the ether bond to be represented by the following general formula: ##STR3## the polymers being produced by polymerization in a thin solution of perfluorodimethylene-bis(perfluorovinyl ether) as the starting material. This cyclic structure in the main chain of the polymer is, however, symmetrical, hence difficulty is accompanied in its synthesis. There is also apprehension such that the polymer is defectively inferior in its solubility and transparency.

It is therefore an object of the present invention to provide a novel fluorine-containing thermoplastic resinous polymer having in the main chain thereof an asymmetrical cyclic structure having the ether bond, which has not been known heretofore.

With a view to solving the above-described problems inherent in the conventional fluorine-containing cyclic polymers, the present invention provides the novel fluorine-containing thermoplastic resinous polymers, as follows:

*a fluorine-containing thermoplastic resinous polymer which consists essentially of a group (a) of repeating units of a cyclic structure to be represented by the following general formula: ##STR4## (where: n is an integer of 1 or 2), said polymer having a molecular weight such that the intrinsic viscosity of the polymer become at least 0.1;

*a fluorine-containing thermoplastic resinous polymer which consists essentially of:

(i) a group (a) of repeating units to be represented by the following general formula: ##STR5## (where: n is an integer of 1 or 2); and

(ii) a group (b) of repeating unit to be represented by the following general formula:

CF.sub.2 --CFX

(where: X is selected from fluorine, chlorine, O--CF2 CF2 CF3, O--CF2 CF(CF3)OCF2 CF2 SO2 F, and O--CF2 CF2 CF2 COOCH3),

said polymer containing therein at least 80% by weight of the group (a) of repeating units, and having a molecular weight such that the intrinsic viscosity of the polymer become at least 0.1.

The group (a) of the repeating units according to the present invention can be obtained by fluorination of a partially fluorinated vinyl ether, for example, CF2 ═CF--O--CF2 CF2 --CH═CH2, after it has been subjected to the cyclic polymerization. Preferably, however, the group (a) of the repeating units can be obtained by subjecting perfluoroallyl vinyl ether (hereinafter abbreviated as "PAVE") or perfluorobutenyl vinyl ether (hereinafter abbreviated as "PBVE"), which is represented by the following general formula:

CF.sub.2 ═CF--O(CF.sub.2).sub.n CF═CF.sub.2

(where: n is an integer of 1 or 2) to the radical cyclic polymerization. In more detail, when PAVE is subjected to the radical polymerization, there is obtained the group (a) of the repeating units, wherein n=1, and, when PBVE is subjected to the radical polymerization, there is obtained the group (a) of the repeating units, wherein n=2.

This discovery is very surprising, because perfluorodiolefin which has so far been known yields a cross-linked polymer in general, while perfluorodimethylene-bis(perfluorovinyl ether), etc. yields a soluble polymer containing the cyclic structure in its main chain, only when it is polymerized in a thin solution.

PAVE is described in Japanese Patent Publication No. 45619/1985. PBVE can be synthesized by de-chlorination of CF2 ═CF--O--CF2 --CF2 --CClF--CClF2 with use of zinc.

More surprising is that PAVE and PBVE are copolymerizable at an arbitrary ratio, hence there can be obtained a copolymer having the repeating units of n=1, n=2 at an arbitrary ratio.

The polymer which contains therein the group (a) of these repeating units is a transparent resin and is soluble in a fluorine type solvent such as perfluoro(2-butyltetrahydrofuran). Also, from the measurement of the infrared ray absorption spectrum, there can be recognized no absorption in the vicinity of 1790 cm-1 due to the double bond.

Incidentally, the preferred cyclic structure to be obtained are those five-membered and six-membered ring structures which has less distortion.

Furthermore, perfluorovinyl ether to be represented by the general formula: CF2 ═CF--O(CF2)n CF═CF2 (where: n is an integer of 1 or 2) is radically copolymerized with a comonomer to be represented by the following general formula: CF2 ═CFX (where: X is selected from fluorine, chlorine, O--CF2 CF2 CF3, O--CF2 CF(CF3)OCF2 CF2 SO2 F, and O--CF2 CF2 CF2 COOCH3) to thereby yield a copolymer which consists essentially of:

(i) a group (a) of repeating units of the cyclic structure to be represented by the following general formula: ##STR6## (where: n is an integer of 1 or 2); and

(ii) a group (b) of repeating units to be represented by the following general formula:

CF.sub.2 --CFX

(where: X is selected from fluorine, chlorine O--CF2 CF2 CF3, O--CF2 CF(CF3)OCF2 CF2 SO2 F, and O--CF2 CF2 CF2 COOCH3).

The comonomer to be represented by the following general formula has already been known:

CF.sub.2 ═CFX

(where: X is selected from fluorine, chlorine, O--CF2 CF2 CF3, O--CF2 CF(CF3)OCF2 CF2 SO2 F, and O--CF2 CF2 CF2 COOCH3).

In order to obtain a transparent and solvent-soluble polymer, it is preferable that 80% by weight or more of the group (a) of the repeating units be contained in the polymer. In case the content of this group (a) of the repeating units is less than 80% by weight, the resin loses its transparency, solvent-solubility and mechanical strength.

Molecular weight of this polymer should preferably be such that its intrinsic viscosity may become 0.1 or above. When the intrinsic viscosity is below 0.1, the mechanical strength of the resin becomes impractically low.

As the method for polymerization of these polymers, there may be employed the radical polymerization. That is to say, the polymerization method is not at all restricted to any specific one, provided that the polymerization proceeds radically. Examples are those polymerizations, in which use is made of an inorganic radical initiator, light rays, ionizing radiation, or heat. The polymerization method is also not particularly limited, and there may be used the bulk-polymerization, solution-polymerization, suspension-polymerization, and emulsion-polymerization.

Molecular weight of the polymer is controllable depending on polymerization temperature, concentration of the initiator, and so on. A chain transfer agent may also be used.

The polymerization composition of the copolymer can be controlled by the charging ratio of each and every comonomer to be used for the polymerization.

Depending on the kind of comonomers to be used and the rate of polymerization, it is possible to regulate the properties of the copolymer resin to be obtained, such as solubility, glass transition point, rupture strength, elongation, yield stress, modulus of elasticity, adhesive to base material, and so forth. Also, depending on the kind of the comonomer, it is possible to control the polymerization speed during the polymerization.

Use of tetrafluoroethylene for the comonomer makes it possible to lower the glass transition temperature of the resulting copolymer and to increase the polymerization speed. Addition of chlorotrifluoroethylene to the comonomer causes solubility of the copolymer to vary. Use of CF2 ═CF--O--CF2 CF2 CF3 as the comonomer improves elongation of the resulting copolymer. When use is made of CF2 ═CF--O--CF2 CF(CF3)--O--CF2 CF2 SO2 F or CF2 ═CF--O--CF2 CF2 CF2 COOCH3 as the comonomer, adhesivity of the resulting copolymer to the base material would increase. It is of course feasible to use two or more kinds of the comonomers.

The polymer consisting of these groups (a) and (b) of the repeating units is transparent, and soluble in those fluorine type solvents such as perfluoro(2-butyltetrahydrofuran), etc. Also, measurement of the infrared ray absorption spectrum reveals no absorption taken place in the vicinity of 1790 cm-1 due to the double bond. The composition of the copolymer is determined by the 19 F--NMR spectrum measurement and the elementary analyses. Incidentally, the preceeding explanations are only for assisting the good understanding of the present invention, hence it goes without saying that they are not intent on limiting the scope of the present invention.

In the following, the present invention will be explained in further details in reference to preferred and actual examples thereof. It should also be understood that these examples are only illustrative of the present invention and do not intend to limit the scope of the present invention.

EXAMPLE 1

30 g of PAVE and 0.3 g of diisopropyl peroxydicarbonate as the polymerization initiator were placed in an ampoule having an inner volume of 100 ml and made of pressure-resistant glass. After repetition of the degassing under freezing condition for two times, the polymerization was conducted for 16 hours at 25° C. The pressure during the polymerization was lower than the atmospheric pressure. After the polymerization reaction, there was obtained 4.5 g of a polymer.

Upon measurement of the infrared ray absorption spectrum of this polymer, there could be observed no absorption in the vicinity of 1790 cm-1 to be derived from the double bond which was present in the starting monomeric substance. Further, when this polymer was dissolved in perfluorobenzene and its 19 F--NMR spectrum was measured, there was obtained a spectrum which indicated to the following repeating structure. ##STR7##

The intrinsic viscosity of this polymer [η] was 0.50 at 30° C. in liquid which is composed principally of "FLORINATE FC-75" (a tradename for perfluoro(2-butyltetrahydrofuran) of 3M Corp., U.S.A. which will hereinafter be abbreviated as "FC-75"). This indicates that the polymer has high degree of polymerization.

The glass transition point of this polymer was 69° C. At a room temperature, this polymer indicated a state of its being tough and transparent glass. Further, its 10% thermal decomposition temperature was 462° C., which indicated that the polymer had high thermal stability. Furthermore, this polymer had colorless transparency, a low refractive index of 1.34, and a high light transmission factor of 95%.

The gas permeability coefficient of this polymer to various gasses was measured, the results of the measurement being shown in the following Table.

______________________________________     Permeation CoefficientGas       (cm.sup.3 cm/cm.sup.2 sec. cm Hg)______________________________________He        106 × 10.sup.-10H.sub.2    26 × 10.sup.-10CO.sub.2   8.2 × 10.sup.-10O.sub.2    3.9 × 10.sup.-10N.sub.2   0.81 × 10.sup.-10CH.sub.4  0.21 × 10.sup.-10______________________________________
EXAMPLE 2

10 g of PAVE, 10 g of trichlorotrifluoroethane (hereinafter abbreviated as "R-113"), and 10 mg of diisopropylperoxydicarbonate as the polymerization initiator were placed in an ampoule having an inner volume of 50 ml and made of pressure-resistant glass. After repetition of the degassing under freezing condition for two times, the polymerization was conducted for 14 hours at 40° C. The pressure during the polymerization was lower than the atmospheric pressure. As the result, there was obtained 6.1 g of a polymer.

The intrinsic viscosity of this polymer [η] was 0.37 at 30° C. in "FC-75", hence the resulted polymer was found to have a high molecular weight. It was also discovered from the 19 F--NMR spectrum measurement that the polymer was similar to that obtained in Example 1 above.

EXAMPLE 3

30 g of PAVE and 10 mg of the polymerization initiator ##STR8## were placed in an ampoule having an inner volume of 50 ml and made of pressure-resistant glass. After repetition of the degassing under freezing condition for two times, the polymerization was conducted for 16 hours at 30° C. The pressure during the polymerization was lower than the atmospheric pressure. After the polymerization reaction, there was obtained 16 g of a polymer.

The intrinsic viscosity of this polymer [η] was 0.505 at 30° C. in "FC-75".

EXAMPLE OF SYNTHESIS 1 (Synthesis of CF2 ═CFCF2 CF2 OCF═CF2)

2,000 g of CF2 ClCFClCF2 COF was reacted with hexafluoropropyleneoxide in the presence of cesium fluoride, and was further converted into potassium salt thereof by use of potassium hydroxide, after which the substance was subjected to thermal decomposition, thereby obtaining CF2 ClCFClCF2 CF2 OCF═CF2 as the product. Subsequently, this product was reacted with a mixture of Zn and dioxane to carry out dechlorination, thereby obtaining 300 g of CF2 ═CFCF2 CF2 OCF═CF2 (PBVE) having boiling point of 64° C. The structure of this fluorine-containing monomer was verified by measurement of 19 F--NMR spectrum.

EXAMPLE 4

5.42 g of PBVE as obtained in the above-described Example of Synthesis 1 and 10 mg of the polymerization initiator ##STR9## were placed in an ampoule having an inner volume of 50 ml and made of pressure-resistant glass. After the degassing under freezing condition was repeated for two times, the polymerization reaction was conducted for 48 hours at 25° C. The pressure during the polymerization reaction was lower than the atmospheric pressure. From this polymerization reaction, there was obtained 2.22 g of a polymer.

When the infrared ray absorption spectrum of this polymer was measured, there could be observed no absorption in the vicinity of 1790 cm-1 to be derived from the double bond which was present in the starting monomeric substance. Further, when this polymer was dissolved in perfluorobenzene and its 19 F--NMR spectrum was measured, there was obtained a spectrum which indicated the following repeating structure. ##STR10##

The intrinsic viscosity of this polymer [η] was 0.55 at 30° C. in "FC-75", which indicated that this polymer had a high degree of polymerization.

The glass transition temperature of this polymer was 108° C. At a room temperature, this polymer indicated at state of its being tough and transparent glass. Also, it had 10% thermal decomposition temperature of 457° C., thus indicating its high thermal stability. By the way, this polymer was colorless transparent, and had its refractive index of as low as 1.34 and its light transmission factor of as high as 95%.

EXAMPLE 5

5 g of PAVE, 5 g of PBVE and 10 mg of the polymerization initiator ##STR11## were placed in a glass reactor having an inner volume of 60 ml. After the degassing under freezing condition for two times, polymerization was conducted for 24 hours at 25° C., while agitating the reactants. The pressure during the polymerization reaction as lower than the atmospheric pressure. As the result, there was obtained 5.5 g of a polymer.

When the infrared ray absorption spectrum of this polymer was measured, there could be observed no absorption in the vicinity of 1790 cm-1 to be derived from the double bond which was present in the starting monomeric substance. Further, this polymer was dissolved in perfluorobenzene and its 19 F--NMR spectrum was measured to verify its structure. As the result, the obtained polymer was found to be a copolymer consisting of: a unit of the cyclic structure to be derived from PAVE such as represented by the following formula: ##STR12## a unit of the cyclic structure to be derived from PBVE such as represented by the following formula: ##STR13## and containing therein 54% by weight of the unit of the cyclic structure to be derived from PAVE.

This polymer was found to have its intrinsic viscosity [η] of 0.44 at 30° C. in "FC-75", hence high degree of polymerization.

The glass transition point of this polymer was 91° C. and indicated a state of its being tough and transparent glass at a room temperature. Further, its 10% thermal decomposition temperature was 435° C., thus indicating that the polymer had high thermal stability. Furthermore, this polymer was colorless transparent, and had its refractive index of as low as 1.34 and its light transmission factor of as high as 95%.

EXAMPLE 6

5 g of PAVE, 15 g of "R-113", and 80 mg of 5 wt % solution of the polymerization initiator ##STR14## were placed in an ampoule having an inner volume of 100 ml and made of pressure-resistant glass. After repetition of the degassing under freezing condition for three times, 0.5 g of CF2 ═CF2 was charged into the reaction system. While shaking the ampoule in an incubator, the polymerization was conducted for six hours at 30° C., as the result of which a solid substance was obtained in quantity of 1.5 g .

The thus obtained solid substance was dissolved in perfluorobenzene, and its structure was verified by measurement of 19 F--NMR spectrum, from which it was found that the resulted polymer was a copolymer consisting of: a unit of the cyclic structure to be derived from PAVE as represented by the following formula: ##STR15## and a unit of the structure to be derived from CF2 ═CF2 as represented by the following formula:

CF.sub.2 --CF.sub.2 ;

and containing therein 81% by weight of the unit of the cyclic structure to be derived from PAVE. Also, this polymer had its intrinsic viscosity [η] of 0.425 at 30° C. in "FC-75".

EXAMPLE 7

20 g of PBVE obtained in Example of Synthesis 1 and 40 mg of the polymerization initiator ##STR16## were placed in an ampoule having an inner volume of 200 ml and made of pressure-resistant glass. After repetition of the degassing under freezing condition for two times, 1.0 g of CF2 ═CFCl was charged into the reaction system. While shaking the ampoule in an incubator, the polymerization reaction was conducted for 10 hours at 25° C. As the result, there was obtained a polymer in a quantity of 4.5 g.

Upon measurement of the infrared ray absorption spectrum of this polymer, it was found that there was no absorption in the vicinity of 1790 cm-1 due to the double bond which was present in the starting monomeric substance. Further, this polymer was dissolved into perfluorobenzene, and its structure was verified by measurement of the 19 F--NMR spectrum. As the result, the thus obtained polymer was found to be a copolymer consisting of: a unit of the cyclic structure to be derived from PBVE such as represented by the following formula: ##STR17## and a unit of the structure to be derived from CF2 ═CFCl as represented by the following formula:

CF.sub.2 --CFCl;

and containing therein 84% by weight of the unit of the cyclic structure to be derived from PBVE. This polymer had its intrinsic viscosity of 0.43 in "FC-75" at 30° C., thus indicating that it had high degree of polymerization.

The polymer was in a state of its being tough and transparent glass at a room temperature. It had also a 10% thermal decomposition temperature of 421° C., which showed that it had high thermal stability. Further, the polymer showed its solubility in a mixed solution of "FC-75" and "R-113".

EXAMPLE 8

20 g of PBVE obtained in Example of Synthesis 1 above and 20 mg of the polymerization initiator ##STR18## were placed in an ampoule having an inner volume of 200 ml and made of pressure-resistant glass. After repetition of the degassing under freezing condition for two times, 0.5 g of CF2 ═CF2 was charged in the reaction system. While shaking this ampoule in an incubator, the polymerization reaction was conducted for five hours at a temperature of 25° C. As the result, there was obtained 5.8 g of a polymer.

Upon measurement of the infrared ray absorption spectrum of this polymer, there could be observed no absorption in the vicinity of 1790 cm-1 to be derived from the double bond which was present in the starting monomeric substance. Further, this polymer was dissolved in perfluorobenzene to measure its 19 F--NMR spectrum, from which its structure was verified. As the result of this, the thus obtained polymer was found to be a copolymer consisting of: a unit of the cyclic structure to be derived from PBVE such as represented by the following formula: ##STR19## and a unit of the structure to be derived from CF2 ═CF2 as represented by the following formula:

CF.sub.2 --CF.sub.2,

and containing therein 94% by weight of the unit of the cyclic structure to be derived from PBVE. Further, this polymer had its intrinsic viscosity [η] of 0.53 in "FC-75" at 30° C., thus indicating that it had high degree of polymerization. It also indicated a state of its being a tough and transparent polymer at a room temperature.

EXAMPLE 9

9 g of PAVE, 1 g of CF2 ═CF--O--CF2 CF2 CF2 COOCH3, and 10 mg of the polymerization initiator ##STR20## were placed in an ampoule having an inner volume of 50 ml and made of pressure-resistant glass. After repetition of the degassing under freezing condition for two times, the polymerization was conducted for 24 hours at a temperature of 25° C. The pressure during the polymerization reaction was lower than the atmospheric pressure. As the result, there was obtained 3.55 g of a polymer.

This polymer was dissolved in perfluorobenzene to measure its 19 F--NMR spectrum, from which its structure was verified. As the result, the thus obtained polymer was found to be a copolymer consisting of a unit of the cyclic structure to be derived from PAVE such as represented by the following formula: ##STR21## a unit of the structure of the formula: ##STR22## and containing therein 93% by weight of the unit of the cyclic structure to be derived from PAVE.

This polymer had its intrinsic viscosity [η] of 0.32 in "FC-75" at 30° C., thus indicating that it had a high degree of polymerization.

The polymer had its glass transition point of 64° C., and indicated a state of its being tough and transparent glass. Also, its 10% thermal decomposition temperature was 430° C., thus indicating that it had high thermal stability. Further, this polymer was colorless transparent.

EXAMPLE 10

40 g of PAVE, 5 g of CF2 ═CF--O--CF2 CF2 CF2 COOCH3, and 10 mg of diisopropyl peroxydicarbonate as the polymerization initiator were placed in an ampoule having an inner volume of 100 ml and made of pressure-resistant glass. After repetition of the degassing under freezing condition for two times, 5 g of CF2 ═CF2 was charged into the reaction system. While shaking this ampoule in an incubator, the polymerization was conducted for 72 hours at a temperature of 30° C. As the result, there was obtained 11.8 g of a polymer.

This polymer was dissolved in perflurobenzene to measure its 19 F--NMR spectrum, from which its structure was verified. As the result, the thus obtained polymer was found to be a copolymer consisting of: a unit of the cyclic structure to be derived from PAVE such as represented by the following formula: ##STR23## and units of the formulas: ##STR24## derived from CF2 ═CF--O--CF2 CF2 CF2 COOCH3 and CF2 ═CF2, respectively, and containing therein 82% by weight of the unit of the cyclic structure to be derived from PAVE.

This polymer had its intrinsic viscosity [η] of 0.42 in "FC-75" at 30° C., thus indicating that it had high degree of polymerization.

The polymer was found to have its glass transition point of 58° C., and indicated a state of its being tough and transparent polymer at a room temperature. Further, its 10% thermal decomposition temperature was 421° C., thus indicating that it had high thermal stability. Furthermore, the polymer was colorless transparent.

EXAMPLE 11

8 g of PBVE, 1 g of CF2 ═CFOCF2 CF(CF3)OCF2 CF2 SO2 F and 10 mg of the polymerization initiator ##STR25## were placed in an ampoule having an inner volume of 50 ml and made of pressure-resistant glass. After repetition of the degassing under freezing condition for two times, polymerization was conducted for 24 hours at 25° C. The pressure during the polymerization reaction was lower than the atmospheric pressure. As the consequence, there was obtained 3.8 g of a polymer. This polymer was dissolved in perfluorobenzene to measure its 19 F--NMR spectrum, from which its structure was verified. As the result, the thus obtained polymer was found to be a copolymer consisting of: a unit of the cyclic structure to be derived from PBVE such as represented by the following formula: ##STR26## and a unit of the structure to be derived from CF2 ═CFOCF2 CF(CF3)OCF2 CF2 SO2 F as represented by the following formula: ##STR27## and containing therein 94% by weight of the unit of the structure to be derived from PBVE.

It was found that this polymer had its intrinsic viscosity [η] of 0.38 in "FC-75" at 30° C., thus indicating that it had high degree of polymerization.

The polymer had its glass transition point of 92° C., and indicated a state of its being tough and transparent glass. The polymer was colorless transparent. The adhesive property of this polymer with glass was satisfactory.

EXAMPLE 12

8 g of PAVE, 2 g of CF2 ═CF--O--CF2 CF2 CF3, and 10 mg of the polymerization initiator ##STR28## were placed in an ampoule having an inner volume of 50 ml and made of pressure-resistant glass. After repetition of the degassing under freezing condition for two times, the polymerization was conducted for 24 hours at a temperature of 25° C. The pressure during the polymerization reaction was lower than the atmospheric pressure. As the result, there was obtained a polymer in a quantity of 1.85 g.

This polymer was dissolved in perfluorobenzene to measure its 19 F--NMR spectrum, from which its structure was verified. As the consequence, the thus obtained polymer was found to be a copolymer consisting of: a unit of the cyclic structure to be derived from PAVE such as represented by the following formula: ##STR29## a unit of the structure to be derived from CF2 ═CF--O--CF2 CF2 CF3 as represented by the following formula: ##STR30## and containing therein 89% by weight of the unit of the cyclic structure to be derived from PAVE.

It was further found that this polymer had its intrinsic viscosity [η] of 0.35 in "FC-75" at 30° C., thus indicating that it had high degree of polymerization.

The polymer had its glass transition point of 61° C., and indicated a state of its being tough and transparent glass. Furthermore, its 10% thermal decomposition temperature was 415° C., thus indicating that the polymer had high thermal stability. Moreover, this polymer was colorless transparent, and showed its elongation of 250% at 25° C.

The fluorine-containing thermoplastic resinous polymer according to the present invention, containing therein the ether bond in its main chain which has not so far been known, can be readily subjected to press-molding, extrusion-molding, and injection-molding, and, when the polymer is molded into optical parts such as lenses, it exhibits remarkable effect such that the molded article is excellent in its transparency, with added superiority in its chemical-resistant property, electrical insulation, heat-stability, strong acid resistant property, strong alkali resistant property, water-resistant property, moisture-resistant property, and so forth. Further, the polymer according to the present invention possesses high transmissibility to the ultraviolet rays, which provides a remarkable effect such that it can substitute various sorts of optical parts made of quartz glass. Furthermore, since it has high transmissibility to the infrared rays, it can be effectively employed for various sorts of infrared ray sensors. Also, the polymer according to the present invention has a low refractive index, in account of which it exhibits an effect such that, when this polymer is prepared into a solution and coated on the surface of the optical parts such as lenses, the light reflection can be reduced. Moreover, the resinous polymer according to the present invention is recognized to be effectively and suitably applicable as the cladding material for the optical fibers, material for opto-magnetic discs, protective membranes for the solar batteries, gas-separating membranes, protective films for transparent resins such as acrylic resin, polycarbonate resin, and diethylene glycol-bis-(allylcarbonate) resin, etc., and treatment agent for textile materials.

Claims (15)

We claim:
1. A fluorine-containing thermoplastic resinous polymer which consists essentially of (a) of repeating units of a cyclic structure represented by the following general formula: ##STR31## where n is an integer of 1 or 2, said polymer having a molecular weight such that the intrinsic viscosity of the polymer is at least 0.1.
2. A polymer according to claim 1, wherein said (a) repeating units are repeating units of cyclically polymerized perfloroallyl vinyl ether and/or perfluorobutenyl vinyl ether.
3. A fluorine-containing thermoplastic resinous polymer which consists essentially of:
(i) (a) of repeating units represented by the following general formula: ##STR32## where n is an integer of 1 or 2, and (ii) (b) of repeating units represented by the following general formula:
CF.sub.2 --CFX
where X is selected from fluorine, chlorine O--CF2 CF2 CF3, O--CF2 CF(CF3)OCF2 CF2 SP2 F, and --CF2 CF2 CF2 COOH3,
said polymer containing therein at least 80% by weight of the repeating units (a), and having a molecular weight such that the intrinsic viscosity of the polymer is at least 0.1.
4. A polymer according to claim 3, wherein said (a) repeating units are repeating units of cyclically polymerized perfluoroallyl vinyl ether and/or perfluorobutenyl vinyl ether.
5. A polymer according to claim 3 or 4, wherein said (b) repeating units are repeating units of a copolymerized comonomer of the following general formula:
CF.sub.2 ═CFX
where X is selected from fluorine, chlorine, O--CF2 CF2 CF3, O--CF2 CF(CF3)OCF2 CF2 SP2 F, and O--CF2 CF2 CF2 COOCH3).
6. A fluorine-containing thermoplastic resinous polymer according to claim 2 wherein the repeating units are: ##STR33##
7. A fluorine containing thermoplastic resinous polymer according to claim 2 wherein the repeating units are: ##STR34##
8. A polymer according to claim 2 which is a copolymer of cyclically polymerized perfluoroallyl vinyl ether and cyclically polymerized perfluorobutenyl vinyl ether.
9. A polymer according to claim 4 which is a copolymer of cyclically polymerized perfluoroallyl vinyl ether and of CF2 ═CF2.
10. A polymer according to claim 4 which is a copolymer of cyclically polymerized perfluorobutenyl vinyl ether and of CF2 ═CFCl.
11. A polymer according to claim 4 which is a copolymer of cyclically polymerized perfluorobutenyl vinyl ether and of CF2 ═CF2.
12. A polymer according to claim 4 which is a copolymer of cyclically polymerized perfluoroallyl vinyl ether and of CF2 ═CF--O--CF2 CF2 CF2 COOCH3.
13. A polymer according to claim 4 which is a terpolymer of cyclically polymerized perfluoroallyl vinyl ether, of CF2 ═CF--O--CF2 CF2 CF2 COOH3 and of CF2 ═CF2.
14. A polymer according to claim 4 which is a copolymer of cyclically polymerized perfluorobutenyl vinyl ether and of CF2 ═CFOCF2 CF(CF3)OCF2 CF2 SO2 F.
15. A polymer according to claim 4 which is a copolymer of cyclically polymerized perfluoroallyl vinyl ether and of CF2 ═CF--O--CF2 CF2 CF3.
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Cited By (72)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5260492A (en) * 1992-12-21 1993-11-09 E. I. Du Pont De Nemours And Company Fluorinated monomers and polymers
EP0568869A2 (en) * 1992-05-05 1993-11-10 E.I. Du Pont De Nemours And Company Amorphous copolymers of two fluorinated ring monomers
US5264508A (en) * 1992-06-25 1993-11-23 The Dow Chemical Company Polymers of haloperfluoro and perfluoro ethers
US5288304A (en) * 1993-03-30 1994-02-22 The University Of Texas System Composite carbon fluid separation membranes
US5326917A (en) * 1992-12-21 1994-07-05 E. I. Du Pont De Nemours And Company Fluorinated monomers and polymers
US5336741A (en) * 1993-12-20 1994-08-09 E. I. Du Pont De Nemours And Company Fluorinated polymer and monomers
US5354910A (en) * 1993-09-07 1994-10-11 E. I. Du Pont De Nemours And Company Functional fluoropolymers
US5364929A (en) * 1993-01-13 1994-11-15 E. I. Du Pont De Nemours And Company Dissolution of tetrafluoroethylene polymers at superautogenous pressure
US5475071A (en) * 1994-09-27 1995-12-12 E. I. Du Pont De Nemours And Company Partially fluorinated polymers and process therefor
US5502132A (en) * 1992-07-27 1996-03-26 Asahi Glass Company Ltd. Process for producing a perfluoro copolymer
US5510406A (en) * 1990-06-01 1996-04-23 Asahi Glass Company, Ltd. Fluoropolymer composition for coating and article coated with the same
US5557018A (en) * 1994-09-27 1996-09-17 E. I. Du Pont De Nemours And Company Partially flourinated polymers and process therefor
US5795668A (en) * 1994-11-10 1998-08-18 E. I. Du Pont De Nemours And Company Fuel cell incorporating a reinforced membrane
US5866285A (en) * 1997-06-12 1999-02-02 Eastman Kodak Company Auxiliary layer for imaging elements containing solvent-soluble fluoropolymer
US5874191A (en) * 1997-06-12 1999-02-23 Eastman Kodak Company Auxiliary layers for imaging elements applied from aqueous coating compositions containing fluoropolymer latex
US5891965A (en) * 1997-01-06 1999-04-06 Dyneon Llc Low temperature perfluoroether-containing fluoroelastomers
US5923805A (en) * 1997-12-22 1999-07-13 Lucent Technologies Inc. Connector for plastic optical fiber
US5966490A (en) * 1997-03-21 1999-10-12 Sdl, Inc. Clad optic fiber, and process for production thereof
US6214955B1 (en) 1996-05-28 2001-04-10 E. I. Du Pont De Nemours And Company Partially fluorinated polymers
US6221987B1 (en) * 1998-04-17 2001-04-24 Asahi Glass Company Ltd. Method for producing a fluorine-containing polymer
US6361583B1 (en) 2000-05-19 2002-03-26 Membrane Technology And Research, Inc. Gas separation using organic-vapor-resistant membranes
US6361582B1 (en) 2000-05-19 2002-03-26 Membrane Technology And Research, Inc. Gas separation using C3+ hydrocarbon-resistant membranes
US6500547B1 (en) 2000-03-06 2002-12-31 General Electric Company Coating materials for sensors and monitoring systems, methods for detecting using sensors and monitoring systems
US6528200B1 (en) * 1996-05-30 2003-03-04 Asahi Glass Company, Ltd. Polymer electrolyte fuel cell, electrode for it and method for producing it
US6544316B2 (en) 2000-05-19 2003-04-08 Membrane Technology And Research, Inc. Hydrogen gas separation using organic-vapor-resistant membranes
US20030073961A1 (en) * 2001-09-28 2003-04-17 Happ Dorrie M. Medical device containing light-protected therapeutic agent and a method for fabricating thereof
US20030100821A1 (en) * 2001-01-02 2003-05-29 Therasense, Inc. Analyte monitoring device and methods of use
US6572679B2 (en) 2000-05-19 2003-06-03 Membrane Technology And Research, Inc. Gas separation using organic-vapor-resistant membranes in conjunction with organic-vapor-selective membranes
US6572680B2 (en) 2000-05-19 2003-06-03 Membrane Technology And Research, Inc. Carbon dioxide gas separation using organic-vapor-resistant membranes
US6579341B2 (en) 2000-05-19 2003-06-17 Membrane Technology And Research, Inc. Nitrogen gas separation using organic-vapor-resistant membranes
US20030125490A1 (en) * 2000-05-31 2003-07-03 Asahi Glass Company Limited Novel fluorinated compound, method for its production and polymer thereof
US6592650B2 (en) 2000-05-19 2003-07-15 Membrane Technology And Research, Inc. Gas separation using organic-vapor-resistant membranes and PSA
US20030181616A1 (en) * 2002-02-12 2003-09-25 Brian Thomas Halogenated monomers and polymers and process for making same
US20030187338A1 (en) * 1998-04-30 2003-10-02 Therasense, Inc. Analyte monitoring device and methods of use
US20030194639A1 (en) * 2002-02-19 2003-10-16 Yoshiko Miya Positive resist composition
US20030198770A1 (en) * 2002-04-18 2003-10-23 3M Innovative Properties Company Composite fluoropolymer-perfluoropolymer assembly
US20030236351A1 (en) * 2002-04-03 2003-12-25 Kouji Toishi Positive resist composition
US20040050250A1 (en) * 2002-07-05 2004-03-18 Membrane Technology And Research, Inc. Gas separation using coated membranes
US6723152B2 (en) 2002-07-01 2004-04-20 Praxair Technology, Inc. Gas separation using membranes formed from blends of perfluorinated polymers
US6747109B2 (en) * 2001-03-08 2004-06-08 Solvay Solexis S.P.A Perfluorodiacylperoxides as polymerization initiators
US6759129B2 (en) 2002-04-18 2004-07-06 3M Innovative Properties Company Adhesion and bonding of multi-layer articles including a fluoropolymer layer
US20040171921A1 (en) * 1998-04-30 2004-09-02 James Say Analyte monitoring device and methods of use
US20040224251A1 (en) * 2002-09-25 2004-11-11 Kouji Toishi Positive resist composition
US6849314B2 (en) 2002-04-18 2005-02-01 3M Innovative Properties Company Fluoropolymer blends and multilayer articles
US20050239156A1 (en) * 2001-04-02 2005-10-27 Therasense, Inc. Blood glucose tracking apparatus and methods
US20060041091A1 (en) * 1999-01-19 2006-02-23 Chang James W Thermoplastic copolymer of tetrafluoroethylene and perfluoromethyl vinyl ether and medical devices employing the copolymer
US20060040098A1 (en) * 2004-08-18 2006-02-23 Imbalzano John F Amphipathic proteinaceous coating on nanoporous polymer
US7005137B1 (en) 2002-06-21 2006-02-28 Advanceed Cardiovascular Systems, Inc. Coating for implantable medical devices
US20060047095A1 (en) * 2004-08-31 2006-03-02 Pacetti Stephen D Polymers of fluorinated monomers and hydrophilic monomers
US20060146388A1 (en) * 2003-09-03 2006-07-06 Aashi Glass Company, Limited Spatial optical modulation element and spatial optical modulation method
US20060194708A1 (en) * 2003-08-08 2006-08-31 Wolfgang Barthel Detergents or cleaning agents
US20060276670A1 (en) * 2005-06-07 2006-12-07 Junk Christopher P Hydrofluoroalkanesulfonic acids from fluorovinyl ethers
US7217426B1 (en) 2002-06-21 2007-05-15 Advanced Cardiovascular Systems, Inc. Coatings containing polycationic peptides for cardiovascular therapy
US7247313B2 (en) 2001-06-27 2007-07-24 Advanced Cardiovascular Systems, Inc. Polyacrylates coatings for implantable medical devices
US20070191700A1 (en) * 1998-04-30 2007-08-16 Abbott Diabetes Care, Inc. Analyte Monitoring Device and Methods of Use
US20080008739A1 (en) * 2006-07-07 2008-01-10 Hossainy Syed F A Phase-separated block copolymer coatings for implantable medical devices
US20080014490A1 (en) * 2000-12-26 2008-01-17 Asahi Glass Company Limited Solid polymer electrolyte material liquid composition, solid polymer fuel cell and fluoropolymer
US20080021436A1 (en) * 1998-04-30 2008-01-24 Abbott Diabetes Care, Inc. Analyte Monitoring Device and Methods of Use
US20080058625A1 (en) * 2006-06-07 2008-03-06 Abbott Diabetes Care, Inc. Analyte monitoring system and method
US20080099400A1 (en) * 2006-10-27 2008-05-01 Cms Technologies Holdings Inc. Removal of Water and Methanol from Fluids
US7396539B1 (en) 2002-06-21 2008-07-08 Advanced Cardiovascular Systems, Inc. Stent coatings with engineered drug release rate
US20090006895A1 (en) * 2001-09-03 2009-01-01 Frank May Method for debugging reconfigurable architectures
US7491233B1 (en) 2002-07-19 2009-02-17 Advanced Cardiovascular Systems Inc. Purified polymers for coatings of implantable medical devices
US20090149568A1 (en) * 2003-05-01 2009-06-11 Abbott Cardiovascular Systems Inc. Biodegradable Coatings For Implantable Medical Devices
US7563454B1 (en) 2003-05-01 2009-07-21 Advanced Cardiovascular Systems, Inc. Coatings for implantable medical devices
US7569275B2 (en) 2002-04-18 2009-08-04 3M Innovative Properties Company Fluoropolymer articles
US20100094111A1 (en) * 1998-04-30 2010-04-15 Abbotte Diabetes Care Inc. Analyte Monitoring Device and Methods of Use
US8048440B2 (en) 2002-08-05 2011-11-01 Gore Enterprise Holdings, Inc. Thermoplastic fluoropolymer-coated medical devices
US8465425B2 (en) 1998-04-30 2013-06-18 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8688188B2 (en) 1998-04-30 2014-04-01 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8974386B2 (en) 1998-04-30 2015-03-10 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US9126137B1 (en) 2012-07-18 2015-09-08 Battelle Memorial Institute Polymer nanocomposites for gas separation

Families Citing this family (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5159038A (en) * 1989-06-09 1992-10-27 Dow Chemical Company Perfluorocyclobutane ring-containing polymers
US5066746A (en) * 1989-06-09 1991-11-19 The Dow Chemical Company Perfluorocyclobutane ring-containing polymers
US5037917A (en) * 1989-06-09 1991-08-06 The Dow Chemical Company Perfluorocyclobutane ring-containing polymers
WO1990015082A1 (en) * 1989-06-09 1990-12-13 The Dow Chemical Company Process for preparing a polymer having perfluorocyclobutane rings and polymers containing perfluorocyclobutane rings
US5021602A (en) * 1989-06-09 1991-06-04 The Dow Chemical Company Reactive compounds containing perfluorocyclobutane rings
US5159037A (en) * 1989-06-09 1992-10-27 The Dow Chemical Company Perfluorocyclobutane ring-containing polymers
US5162468A (en) * 1989-06-09 1992-11-10 The Dow Chemical Company Perfluorovinyl compounds
US5364547A (en) * 1989-06-09 1994-11-15 The Dow Chemical Company Lubricants containing perfluorocyclobutane rings
US5210265A (en) * 1989-06-09 1993-05-11 The Dow Chemical Company Reactive compounds containing perfluorocyclobutane rings
US5198513A (en) * 1989-06-09 1993-03-30 The Dow Chemical Company Reactive compounds containing perfluorovinyl groups
US5364917A (en) * 1989-06-09 1994-11-15 The Dow Chemical Company Perfluorocyclobutane ring-containing polymers
US5037919A (en) * 1989-06-09 1991-08-06 The Dow Chemical Company Reactive compounds containing perfluorovinyl groups
US5159036A (en) * 1989-12-15 1992-10-27 The Dow Chemical Company Perfluorocyclobutane ring-containing polymers with crosslinking
US5037918A (en) * 1989-12-15 1991-08-06 The Dow Chemical Company Perfluorocyclobutane ring-containing polymers with crosslinking
JP2821935B2 (en) * 1990-04-19 1998-11-05 三菱レイヨン 株式会社 Plastic optical fiber
DE69130280D1 (en) * 1990-10-16 1998-11-05 Mitsui Chemicals Inc Use of a highly light-transmitting dust protective film, process for its preparation and dust protective member
US5139597A (en) * 1990-10-26 1992-08-18 Moore Business Forms, Inc. Detacher to folder or pressure sealer shingle conveyor
US5730922A (en) * 1990-12-10 1998-03-24 The Dow Chemical Company Resin transfer molding process for composites
US5246782A (en) * 1990-12-10 1993-09-21 The Dow Chemical Company Laminates of polymers having perfluorocyclobutane rings and polymers containing perfluorocyclobutane rings
DE4219764A1 (en) * 1992-06-17 1993-12-23 Bayer Ag Cyclopolymerize fluorine compounds, processes for their preparation and obtainable therefrom thermoplastic fluoropolymers
US5449825A (en) * 1992-06-25 1995-09-12 The Dow Chemical Company Preparation of haloperfluoro and perfluoro ethers
US5583035A (en) * 1992-12-07 1996-12-10 Bayer Aktiengesellschaft HIV antisense expression vectors
DK0683181T3 (en) * 1994-05-19 1997-10-13 Ausimont Spa Fluorinated polymers and copolymers containing cyclic structures.
DE69914538D1 (en) * 1998-06-30 2004-03-11 Solvay Solexis Spa Cleaning of fluoropolymers
EP1057521B1 (en) 1999-05-25 2004-07-28 Solvay Solexis S.p.A. Membranes of (per)fluorinated amorphous polymers
EP1174448B1 (en) 2000-07-20 2004-09-29 Solvay Solexis S.p.A. Fine powders of polytetrafluoroethylene
US6414202B1 (en) 2000-08-30 2002-07-02 Membrane Technology And Research, Inc. Membrane-augmented manufacture of propylene derivatives
US6271319B1 (en) 2000-08-30 2001-08-07 Membrane Technology And Research, Inc. Membrane-augmented polypropylene manufacturing
WO2003037838A1 (en) * 2001-10-31 2003-05-08 Asahi Glass Company, Limited Fluorine-containing diene compounds, fluoropolymers and processes for production of both
CN100528823C (en) * 2001-12-12 2009-08-19 旭硝子株式会社 Process for producing diene compound
US20040063805A1 (en) * 2002-09-19 2004-04-01 Pacetti Stephen D. Coatings for implantable medical devices and methods for fabrication thereof
US9114198B2 (en) * 2003-11-19 2015-08-25 Advanced Cardiovascular Systems, Inc. Biologically beneficial coatings for implantable devices containing fluorinated polymers and methods for fabricating the same
JP4789944B2 (en) * 2004-09-21 2011-10-12 ソルヴェイ ソレクシス エス.ピー.エー.Solvay Solexis S.p.A. Use of the perfluoropolymer latex submicron in measuring molecular interactions by laser light scattering (lls)
EP1970407B1 (en) * 2006-01-05 2013-03-27 Asahi Glass Company, Limited Fluorine-containing polymer and fluorine-containing polymer composition containing same
KR20080086974A (en) * 2006-01-27 2008-09-29 아사히 가라스 가부시키가이샤 Fluoropolymer for chromatic aberration correction lens, and chromatic aberration correction lens
JP4950229B2 (en) * 2006-03-16 2012-06-13 ソルヴェイ ソレクシス エス.ピー.エー.Solvay Solexis S.p.A. Receptor - the use of the perfluoropolymer in the measurement of ligand binding constants
US8002874B2 (en) * 2007-03-06 2011-08-23 Membrane Technology And Research, Inc. Liquid-phase and vapor-phase dehydration of organic/water solutions
CN101646696B (en) 2007-03-30 2012-07-04 旭硝子株式会社 Novel fluorine-containing compound, fluorine-containing polymer, and method for producing the compound
GB0709033D0 (en) * 2007-05-11 2007-06-20 3M Innovative Properties Co Melt-Processible fluoropolymers having long-chain branches, Methods of preparing them and uses thereof
GB0801194D0 (en) * 2008-01-23 2008-02-27 3M Innovative Properties Co Processing aid compositions comprising fluoropolymers having long-chain branches
EP2722350A1 (en) * 2012-10-19 2014-04-23 Solvay Specialty Polymers Italy S.p.A. Amorphous fluorinated polymer
CN105283475A (en) 2013-06-14 2016-01-27 3M创新有限公司 Fluoropolymers comprising monomeric units derived from a vinyl perfluoroalkyl or vinyl perfluoroalkylenoxide perfluorovinyl ether
EP3080174A2 (en) 2013-12-11 2016-10-19 3M Innovative Properties Company Highly fluorinated elastomers
WO2016087439A1 (en) 2014-12-05 2016-06-09 Solvay Specialty Polymers Italy S.P.A. One-dimensional planar photonic crystals including fluoropolymer compositions and corresponding fabrication methods

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3084144A (en) * 1956-07-02 1963-04-02 Minnesota Mining & Mfg Process for polymerization of fluorinecontaining organic compounds
US3274265A (en) * 1961-11-27 1966-09-20 Nat Res Dev Fluorinated organic compounds
GB1106344A (en) * 1965-03-29 1968-03-13 Du Pont Perfluorocyclic ether polymers
US3418302A (en) * 1963-08-30 1968-12-24 Du Pont Perfluorocyclic ether polymers
US4209635A (en) * 1979-03-02 1980-06-24 Asahi Glass Company Limited Process for producing perfluorinated vinyl ether having ester group

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3114778A (en) * 1963-12-17 Fluorinated vinyl ethers and their
US2729613A (en) * 1951-02-19 1956-01-03 William T Miller Solid polymers of perhalogenated polyolefins
US2917496A (en) * 1954-10-20 1959-12-15 Minnesota Mining & Mfg Copolymer of a fluoro-butadiene and an acrylic comonomer and process of making same
US2975163A (en) * 1956-10-29 1961-03-14 Minnesota Mining & Mfg Fluorine containing organic compounds and preparation thereof
US3310606A (en) * 1963-08-28 1967-03-21 Du Pont Thermosetting perfluorinated divinyl ether resins
US3397191A (en) * 1965-06-02 1968-08-13 Du Pont Fluorocarbon ethers
US3418382A (en) * 1965-12-10 1968-12-24 Universal Oil Prod Co Conversion of mercaptans to alcohols
JPS5222599A (en) * 1975-08-15 1977-02-19 Asahi Glass Co Ltd Production of alkali hydroxide
JP2524123B2 (en) * 1986-08-18 1996-08-14 日本メクトロン株式会社 Preparation of the fluorine-containing copolymer
JPS63238115A (en) * 1987-03-27 1988-10-04 Asahi Glass Co Ltd Production of fluorine-containing copolymer having cyclic structure
JP2724709B2 (en) * 1987-04-20 1998-03-09 旭硝子株式会社 Kuratsudo material for optical transmission Fuaiba

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3084144A (en) * 1956-07-02 1963-04-02 Minnesota Mining & Mfg Process for polymerization of fluorinecontaining organic compounds
US3274265A (en) * 1961-11-27 1966-09-20 Nat Res Dev Fluorinated organic compounds
US3418302A (en) * 1963-08-30 1968-12-24 Du Pont Perfluorocyclic ether polymers
GB1106344A (en) * 1965-03-29 1968-03-13 Du Pont Perfluorocyclic ether polymers
US4209635A (en) * 1979-03-02 1980-06-24 Asahi Glass Company Limited Process for producing perfluorinated vinyl ether having ester group

Cited By (222)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5510406A (en) * 1990-06-01 1996-04-23 Asahi Glass Company, Ltd. Fluoropolymer composition for coating and article coated with the same
US5326839A (en) * 1992-05-05 1994-07-05 E. I. Du Pont De Nemours And Company Amorphous copolymers of two fluorinated ring monomers
EP0568869A2 (en) * 1992-05-05 1993-11-10 E.I. Du Pont De Nemours And Company Amorphous copolymers of two fluorinated ring monomers
US5338608A (en) * 1992-05-05 1994-08-16 E. I. Du Pont De Nemours And Company Amorphous copolymers of two fluorinated ring monomers
US5276121A (en) * 1992-05-05 1994-01-04 E. I. Du Pont De Nemours And Company Amorphous copolymers of two fluorinated ring monomers
EP0568869A3 (en) * 1992-05-05 1994-06-22 Du Pont Amorphous copolymers of two fluorinated ring monomers
US5324889A (en) * 1992-05-05 1994-06-28 E. I. Du Pont De Nemours And Company Amorphous copolymers of two fluorinated ring monomers
US5353368A (en) * 1992-05-05 1994-10-04 E. I. Du Pont De Nemours And Company Optical fiber comprising a cladding made of amorphous copolymers of two fluorinated ring monomers
US5264508A (en) * 1992-06-25 1993-11-23 The Dow Chemical Company Polymers of haloperfluoro and perfluoro ethers
US5393852A (en) * 1992-06-25 1995-02-28 The Dow Chemical Company Polymers of haloperfluoro and perfluoro ethers
US5502132A (en) * 1992-07-27 1996-03-26 Asahi Glass Company Ltd. Process for producing a perfluoro copolymer
US5326917A (en) * 1992-12-21 1994-07-05 E. I. Du Pont De Nemours And Company Fluorinated monomers and polymers
WO1994014741A1 (en) * 1992-12-21 1994-07-07 E.I. Du Pont De Nemours And Company Fluorinated monomers and polymers
US5350821A (en) * 1992-12-21 1994-09-27 E. I. Du Pont De Nemours And Company Fluorinated monomers and polymers
US5260492A (en) * 1992-12-21 1993-11-09 E. I. Du Pont De Nemours And Company Fluorinated monomers and polymers
US5364929A (en) * 1993-01-13 1994-11-15 E. I. Du Pont De Nemours And Company Dissolution of tetrafluoroethylene polymers at superautogenous pressure
WO1994022561A1 (en) * 1993-03-30 1994-10-13 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Composite carbon fluid separation membranes
US5288304A (en) * 1993-03-30 1994-02-22 The University Of Texas System Composite carbon fluid separation membranes
US5354910A (en) * 1993-09-07 1994-10-11 E. I. Du Pont De Nemours And Company Functional fluoropolymers
US5401886A (en) * 1993-12-20 1995-03-28 E. I. Du Pont De Nemours And Company Fluorinated polymer and monomers
US5336741A (en) * 1993-12-20 1994-08-09 E. I. Du Pont De Nemours And Company Fluorinated polymer and monomers
US5475071A (en) * 1994-09-27 1995-12-12 E. I. Du Pont De Nemours And Company Partially fluorinated polymers and process therefor
US5557018A (en) * 1994-09-27 1996-09-17 E. I. Du Pont De Nemours And Company Partially flourinated polymers and process therefor
US5795668A (en) * 1994-11-10 1998-08-18 E. I. Du Pont De Nemours And Company Fuel cell incorporating a reinforced membrane
US6214955B1 (en) 1996-05-28 2001-04-10 E. I. Du Pont De Nemours And Company Partially fluorinated polymers
US6528200B1 (en) * 1996-05-30 2003-03-04 Asahi Glass Company, Ltd. Polymer electrolyte fuel cell, electrode for it and method for producing it
US6734132B2 (en) 1996-05-30 2004-05-11 Asahi Glass Company, Ltd. Polymer electrolyte fuel cell, electrode for it and method for producing it
US5891965A (en) * 1997-01-06 1999-04-06 Dyneon Llc Low temperature perfluoroether-containing fluoroelastomers
US5966490A (en) * 1997-03-21 1999-10-12 Sdl, Inc. Clad optic fiber, and process for production thereof
US5874191A (en) * 1997-06-12 1999-02-23 Eastman Kodak Company Auxiliary layers for imaging elements applied from aqueous coating compositions containing fluoropolymer latex
US5866285A (en) * 1997-06-12 1999-02-02 Eastman Kodak Company Auxiliary layer for imaging elements containing solvent-soluble fluoropolymer
US5923805A (en) * 1997-12-22 1999-07-13 Lucent Technologies Inc. Connector for plastic optical fiber
US6221987B1 (en) * 1998-04-17 2001-04-24 Asahi Glass Company Ltd. Method for producing a fluorine-containing polymer
US8612159B2 (en) 1998-04-30 2013-12-17 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US9066694B2 (en) 1998-04-30 2015-06-30 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US9066697B2 (en) 1998-04-30 2015-06-30 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US9066695B2 (en) 1998-04-30 2015-06-30 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US9042953B2 (en) 1998-04-30 2015-05-26 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US9011331B2 (en) 1998-04-30 2015-04-21 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US9014773B2 (en) 1998-04-30 2015-04-21 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8974386B2 (en) 1998-04-30 2015-03-10 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8880137B2 (en) 1998-04-30 2014-11-04 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8840553B2 (en) 1998-04-30 2014-09-23 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8774887B2 (en) 1998-04-30 2014-07-08 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US20030187338A1 (en) * 1998-04-30 2003-10-02 Therasense, Inc. Analyte monitoring device and methods of use
US8744545B2 (en) 1998-04-30 2014-06-03 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8734346B2 (en) 1998-04-30 2014-05-27 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8734348B2 (en) 1998-04-30 2014-05-27 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8738109B2 (en) 1998-04-30 2014-05-27 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8688188B2 (en) 1998-04-30 2014-04-01 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US9072477B2 (en) 1998-04-30 2015-07-07 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8672844B2 (en) 1998-04-30 2014-03-18 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8670815B2 (en) 1998-04-30 2014-03-11 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8666469B2 (en) 1998-04-30 2014-03-04 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US20040171921A1 (en) * 1998-04-30 2004-09-02 James Say Analyte monitoring device and methods of use
US8660627B2 (en) 1998-04-30 2014-02-25 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8649841B2 (en) 1998-04-30 2014-02-11 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8641619B2 (en) 1998-04-30 2014-02-04 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8622906B2 (en) 1998-04-30 2014-01-07 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US20050199494A1 (en) * 1998-04-30 2005-09-15 James Say Analyte monitoring device and methods of use
US8617071B2 (en) 1998-04-30 2013-12-31 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US9326714B2 (en) 1998-04-30 2016-05-03 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8597189B2 (en) 1998-04-30 2013-12-03 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8480580B2 (en) 1998-04-30 2013-07-09 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8473021B2 (en) 1998-04-30 2013-06-25 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8465425B2 (en) 1998-04-30 2013-06-18 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8409131B2 (en) 1998-04-30 2013-04-02 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8391945B2 (en) 1998-04-30 2013-03-05 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8380273B2 (en) 1998-04-30 2013-02-19 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8372005B2 (en) 1998-04-30 2013-02-12 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8366614B2 (en) 1998-04-30 2013-02-05 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8357091B2 (en) 1998-04-30 2013-01-22 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8353829B2 (en) 1998-04-30 2013-01-15 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8346336B2 (en) 1998-04-30 2013-01-01 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US20070149873A1 (en) * 1998-04-30 2007-06-28 Abbott Diabetes Care, Inc. Analyte Monitoring Device and Methods of Use
US20070161879A1 (en) * 1998-04-30 2007-07-12 Abbott Diabetes Care, Inc. Analyte Monitoring Device and Methods of Use
US20070161880A1 (en) * 1998-04-30 2007-07-12 Abbott Diabetes Care, Inc. Analyte Monitoring Device and Methods of Use
US8306598B2 (en) 1998-04-30 2012-11-06 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8287454B2 (en) 1998-04-30 2012-10-16 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US20070179372A1 (en) * 1998-04-30 2007-08-02 Abbott Diabetes Care, Inc. Analyte Monitoring Device and Methods of Use
US20070191700A1 (en) * 1998-04-30 2007-08-16 Abbott Diabetes Care, Inc. Analyte Monitoring Device and Methods of Use
US20070213610A1 (en) * 1998-04-30 2007-09-13 Abbott Diabetes Care, Inc. Analyte Monitoring Device and Methods of Use
US8273022B2 (en) 1998-04-30 2012-09-25 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8275439B2 (en) 1998-04-30 2012-09-25 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8265726B2 (en) 1998-04-30 2012-09-11 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US20080021436A1 (en) * 1998-04-30 2008-01-24 Abbott Diabetes Care, Inc. Analyte Monitoring Device and Methods of Use
US8260392B2 (en) 1998-04-30 2012-09-04 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8255031B2 (en) 1998-04-30 2012-08-28 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8235896B2 (en) 1998-04-30 2012-08-07 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8231532B2 (en) 1998-04-30 2012-07-31 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8226558B2 (en) 1998-04-30 2012-07-24 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8226555B2 (en) 1998-04-30 2012-07-24 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8226557B2 (en) 1998-04-30 2012-07-24 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8224413B2 (en) 1998-04-30 2012-07-17 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US20080167543A1 (en) * 1998-04-30 2008-07-10 Abbott Diabetes Care, Inc. Analyte Monitoring Device And Methods Of Use
US20080262329A1 (en) * 1998-04-30 2008-10-23 Abbott Diabetes Care, Inc. Analyte Monitoring Device and Methods of Use
US8177716B2 (en) 1998-04-30 2012-05-15 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8175673B2 (en) 1998-04-30 2012-05-08 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8162829B2 (en) 1998-04-30 2012-04-24 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US7885699B2 (en) 1998-04-30 2011-02-08 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US20110011399A1 (en) * 1998-04-30 2011-01-20 Abbott Diabetes Care Inc. Analyte Monitoring Device and Methods of Use
US20110015510A1 (en) * 1998-04-30 2011-01-20 Abbott Diabetes Care Inc. Analyte Monitoring Device and Methods of Use
US20090177057A1 (en) * 1998-04-30 2009-07-09 Abbott Diabetes Care, Inc. Analyte Monitoring Device and Methods of Use
US20090173628A1 (en) * 1998-04-30 2009-07-09 Abbott Diabetes Care, Inc. Analyte Monitoring Device and Methods of Use
US20090182215A1 (en) * 1998-04-30 2009-07-16 Abbott Diabetes Care Inc. Analyte Monitoring Device and Methods of Use
US7869853B1 (en) 1998-04-30 2011-01-11 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US20090187090A1 (en) * 1998-04-30 2009-07-23 Abbott Diabetes Care Inc. Analyte Monitoring Device and Methods of Use
US7860544B2 (en) 1998-04-30 2010-12-28 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US20090216101A1 (en) * 1998-04-30 2009-08-27 Abbott Diabetes Care, Inc. Analyte Monitoring Device and Methods of Use
US20100324400A1 (en) * 1998-04-30 2010-12-23 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US20090292189A1 (en) * 1998-04-30 2009-11-26 Abbott Diabetes Care Inc. Analyte Monitoring Device and Methods of Use
US20100268050A1 (en) * 1998-04-30 2010-10-21 Abbott Diabetes Care Inc. Analyte Monitoring Device and Methods of Use
US20100069729A1 (en) * 1998-04-30 2010-03-18 James Say Analyte Monitoring Device And Methods Of Use
US20100324399A1 (en) * 1998-04-30 2010-12-23 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US20100094111A1 (en) * 1998-04-30 2010-04-15 Abbotte Diabetes Care Inc. Analyte Monitoring Device and Methods of Use
US20100292553A1 (en) * 1998-04-30 2010-11-18 Abbott Diabetes Care Inc. Analyte Monitoring Device and Methods of Use
US20100268044A1 (en) * 1998-04-30 2010-10-21 Abbott Diabetes Care Inc. Analyte Monitoring Device and Methods of Use
US20100268046A1 (en) * 1998-04-30 2010-10-21 James Say Analyte Monitoring Device and Methods of Use
US20100168658A1 (en) * 1998-04-30 2010-07-01 Abbott Diabetes Care Inc. Analyte Monitoring Device and Methods of Use
US20100168659A1 (en) * 1998-04-30 2010-07-01 Abbott Diabetes Care Inc. Analyte Monitoring Device and Methods of Use
US20100268045A1 (en) * 1998-04-30 2010-10-21 Abbott Diabetes Care Inc. Analyte Monitoring Device and Methods of Use
US20100234709A1 (en) * 1998-04-30 2010-09-16 Abbott Diabetes Care Inc. Analyte Monitoring Device and Methods of Use
US8346337B2 (en) 1998-04-30 2013-01-01 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US20060041091A1 (en) * 1999-01-19 2006-02-23 Chang James W Thermoplastic copolymer of tetrafluoroethylene and perfluoromethyl vinyl ether and medical devices employing the copolymer
US7462675B2 (en) 1999-01-19 2008-12-09 Gore Enterprise Holdings, Inc. Thermoplastic copolymer of tetrafluoroethylene and perfluoromethyl vinyl ether and medical devices employing the copolymer
US6500547B1 (en) 2000-03-06 2002-12-31 General Electric Company Coating materials for sensors and monitoring systems, methods for detecting using sensors and monitoring systems
US6361582B1 (en) 2000-05-19 2002-03-26 Membrane Technology And Research, Inc. Gas separation using C3+ hydrocarbon-resistant membranes
US6572680B2 (en) 2000-05-19 2003-06-03 Membrane Technology And Research, Inc. Carbon dioxide gas separation using organic-vapor-resistant membranes
US6544316B2 (en) 2000-05-19 2003-04-08 Membrane Technology And Research, Inc. Hydrogen gas separation using organic-vapor-resistant membranes
US6361583B1 (en) 2000-05-19 2002-03-26 Membrane Technology And Research, Inc. Gas separation using organic-vapor-resistant membranes
US6572679B2 (en) 2000-05-19 2003-06-03 Membrane Technology And Research, Inc. Gas separation using organic-vapor-resistant membranes in conjunction with organic-vapor-selective membranes
US6592650B2 (en) 2000-05-19 2003-07-15 Membrane Technology And Research, Inc. Gas separation using organic-vapor-resistant membranes and PSA
US6579341B2 (en) 2000-05-19 2003-06-17 Membrane Technology And Research, Inc. Nitrogen gas separation using organic-vapor-resistant membranes
US20030125490A1 (en) * 2000-05-31 2003-07-03 Asahi Glass Company Limited Novel fluorinated compound, method for its production and polymer thereof
US6756458B2 (en) 2000-05-31 2004-06-29 Asahi Glass Company, Limited Fluorinated compound, method for its production and polymer thereof
US20080014490A1 (en) * 2000-12-26 2008-01-17 Asahi Glass Company Limited Solid polymer electrolyte material liquid composition, solid polymer fuel cell and fluoropolymer
US8263710B2 (en) 2000-12-26 2012-09-11 Asahi Glass Company, Limited Solid polymer electrolyte material, liquid composition, solid polymer fuel cell and fluoropolymer
US8470943B2 (en) 2000-12-26 2013-06-25 Asahi Glass Company, Limited Solid polymer electrolyte material, liquid composition, solid polymer fuel cell and fluoropolymer
US8043763B2 (en) 2000-12-26 2011-10-25 Asahi Glass Company, Limited Solid polymer electrolyte material, liquid composition, solid polymer fuel cell and fluoropolymer
US20080086040A1 (en) * 2001-01-02 2008-04-10 Abbott Diabetes Care, Inc. Analyte Monitoring Device And Methods Of Use
US9011332B2 (en) 2001-01-02 2015-04-21 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US20080086043A1 (en) * 2001-01-02 2008-04-10 Abbott Diabetes Care, Inc. Analyte Monitoring Device And Methods Of Use
US9498159B2 (en) 2001-01-02 2016-11-22 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8668645B2 (en) 2001-01-02 2014-03-11 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US20080091095A1 (en) * 2001-01-02 2008-04-17 Abbott Diabetes Care, Inc. Analyte Monitoring Device And Methods Of Use
US9610034B2 (en) 2001-01-02 2017-04-04 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US20080086041A1 (en) * 2001-01-02 2008-04-10 Abbott Diabetes Care, Inc. Analyte Monitoring Device And Methods Of Use
US20030100821A1 (en) * 2001-01-02 2003-05-29 Therasense, Inc. Analyte monitoring device and methods of use
US8652043B2 (en) 2001-01-02 2014-02-18 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US6747109B2 (en) * 2001-03-08 2004-06-08 Solvay Solexis S.P.A Perfluorodiacylperoxides as polymerization initiators
US20100098583A1 (en) * 2001-04-02 2010-04-22 Abbott Diabetes Care Inc. Blood Glucose Tracking Apparatus and Methods
US9477811B2 (en) 2001-04-02 2016-10-25 Abbott Diabetes Care Inc. Blood glucose tracking apparatus and methods
US7976778B2 (en) 2001-04-02 2011-07-12 Abbott Diabetes Care Inc. Blood glucose tracking apparatus
US8236242B2 (en) 2001-04-02 2012-08-07 Abbott Diabetes Care Inc. Blood glucose tracking apparatus and methods
US8765059B2 (en) 2001-04-02 2014-07-01 Abbott Diabetes Care Inc. Blood glucose tracking apparatus
US20100145733A1 (en) * 2001-04-02 2010-06-10 Abbott Diabetes Care Inc. Blood Glucose Tracking Apparatus and Methods
US20100311151A1 (en) * 2001-04-02 2010-12-09 Abbott Diabetes Care Inc. Blood Glucose Tracking Apparatus and Methods
US20050277164A1 (en) * 2001-04-02 2005-12-15 Therasense, Inc. Blood glucose tracking apparatus and methods
US20050239156A1 (en) * 2001-04-02 2005-10-27 Therasense, Inc. Blood glucose tracking apparatus and methods
US8268243B2 (en) 2001-04-02 2012-09-18 Abbott Diabetes Care Inc. Blood glucose tracking apparatus and methods
US20100100580A1 (en) * 2001-04-02 2010-04-22 Abbott Diabetes Care Inc. Blood Glucose Tracking Apparatus and Methods
US20100068796A1 (en) * 2001-04-02 2010-03-18 Abbott Diabetes Care Inc. Blood Glucose Tracking Apparatus and Methods
US7247313B2 (en) 2001-06-27 2007-07-24 Advanced Cardiovascular Systems, Inc. Polyacrylates coatings for implantable medical devices
US20090006895A1 (en) * 2001-09-03 2009-01-01 Frank May Method for debugging reconfigurable architectures
US20030073961A1 (en) * 2001-09-28 2003-04-17 Happ Dorrie M. Medical device containing light-protected therapeutic agent and a method for fabricating thereof
US20030181616A1 (en) * 2002-02-12 2003-09-25 Brian Thomas Halogenated monomers and polymers and process for making same
US20030194639A1 (en) * 2002-02-19 2003-10-16 Yoshiko Miya Positive resist composition
US20030236351A1 (en) * 2002-04-03 2003-12-25 Kouji Toishi Positive resist composition
US7129014B2 (en) 2002-04-03 2006-10-31 Sumitomo Chemical Company, Limited Positive resist composition
US6849314B2 (en) 2002-04-18 2005-02-01 3M Innovative Properties Company Fluoropolymer blends and multilayer articles
US6759129B2 (en) 2002-04-18 2004-07-06 3M Innovative Properties Company Adhesion and bonding of multi-layer articles including a fluoropolymer layer
US7569275B2 (en) 2002-04-18 2009-08-04 3M Innovative Properties Company Fluoropolymer articles
US20050124717A1 (en) * 2002-04-18 2005-06-09 3M Innovative Properties Company Fluoropolymer blends and multilayer articles
US20030198770A1 (en) * 2002-04-18 2003-10-23 3M Innovative Properties Company Composite fluoropolymer-perfluoropolymer assembly
US7803394B2 (en) 2002-06-21 2010-09-28 Advanced Cardiovascular Systems, Inc. Polycationic peptide hydrogel coatings for cardiovascular therapy
US7396539B1 (en) 2002-06-21 2008-07-08 Advanced Cardiovascular Systems, Inc. Stent coatings with engineered drug release rate
US7217426B1 (en) 2002-06-21 2007-05-15 Advanced Cardiovascular Systems, Inc. Coatings containing polycationic peptides for cardiovascular therapy
US7901703B2 (en) 2002-06-21 2011-03-08 Advanced Cardiovascular Systems, Inc. Polycationic peptides for cardiovascular therapy
US20090005861A1 (en) * 2002-06-21 2009-01-01 Hossainy Syed F A Stent coatings with engineered drug release rate
US7005137B1 (en) 2002-06-21 2006-02-28 Advanceed Cardiovascular Systems, Inc. Coating for implantable medical devices
US6723152B2 (en) 2002-07-01 2004-04-20 Praxair Technology, Inc. Gas separation using membranes formed from blends of perfluorinated polymers
US20040050250A1 (en) * 2002-07-05 2004-03-18 Membrane Technology And Research, Inc. Gas separation using coated membranes
US6896717B2 (en) 2002-07-05 2005-05-24 Membrane Technology And Research, Inc. Gas separation using coated membranes
US7491233B1 (en) 2002-07-19 2009-02-17 Advanced Cardiovascular Systems Inc. Purified polymers for coatings of implantable medical devices
US8048440B2 (en) 2002-08-05 2011-11-01 Gore Enterprise Holdings, Inc. Thermoplastic fluoropolymer-coated medical devices
US8609125B2 (en) 2002-08-05 2013-12-17 W. L. Gore & Associates, Inc. Thermoplastic fluoropolymer-coated medical devices
US20070088131A1 (en) * 2002-09-25 2007-04-19 Kouji Toishi Sulfonate and resist composition
US20040224251A1 (en) * 2002-09-25 2004-11-11 Kouji Toishi Positive resist composition
US7563454B1 (en) 2003-05-01 2009-07-21 Advanced Cardiovascular Systems, Inc. Coatings for implantable medical devices
US8791171B2 (en) 2003-05-01 2014-07-29 Abbott Cardiovascular Systems Inc. Biodegradable coatings for implantable medical devices
US20090149568A1 (en) * 2003-05-01 2009-06-11 Abbott Cardiovascular Systems Inc. Biodegradable Coatings For Implantable Medical Devices
US20060194708A1 (en) * 2003-08-08 2006-08-31 Wolfgang Barthel Detergents or cleaning agents
US7453620B2 (en) 2003-09-03 2008-11-18 Asahi Glass Company, Limited Spatial optical modulation element and spatial optical modulation method
US20060146388A1 (en) * 2003-09-03 2006-07-06 Aashi Glass Company, Limited Spatial optical modulation element and spatial optical modulation method
US7147912B2 (en) 2004-08-18 2006-12-12 E. I. Du Pont De Nemours And Company Amphipathic proteinaceous coating on nanoporous polymer
US20060040098A1 (en) * 2004-08-18 2006-02-23 Imbalzano John F Amphipathic proteinaceous coating on nanoporous polymer
US20070228345A1 (en) * 2004-08-31 2007-10-04 Advanced Cardiovascular Systems, Inc. Polymers of fluorinated monomers and hydrophilic monomers
US20060047095A1 (en) * 2004-08-31 2006-03-02 Pacetti Stephen D Polymers of fluorinated monomers and hydrophilic monomers
US20060269586A1 (en) * 2004-08-31 2006-11-30 Advanced Cardiovascular Systems, Inc. Polymers of fluorinated monomers and hydrophilic monomers
US7244443B2 (en) 2004-08-31 2007-07-17 Advanced Cardiovascular Systems, Inc. Polymers of fluorinated monomers and hydrophilic monomers
US7766884B2 (en) 2004-08-31 2010-08-03 Advanced Cardiovascular Systems, Inc. Polymers of fluorinated monomers and hydrophilic monomers
US7357793B2 (en) 2004-08-31 2008-04-15 Advanced Cardiovascular Systems, Inc. Polymers of fluorinated and hydrophilic monomers
US8048604B2 (en) 2005-06-07 2011-11-01 E.I.Du Pont De Nemours And Company Hydrofluoroalkanesulfonic acids and salts from fluorovinyl ethers
US20060276670A1 (en) * 2005-06-07 2006-12-07 Junk Christopher P Hydrofluoroalkanesulfonic acids from fluorovinyl ethers
US7834209B2 (en) 2005-06-07 2010-11-16 E.I. Du Pont De Nemours And Company Hydrofluoroalkanesulfonic acids from fluorovinyl ethers
US20110039203A1 (en) * 2005-06-07 2011-02-17 E. I. Du Pont De Nemours And Company Hydrofluoroalkanesulfonic Acids and Salts from Fluorovinyl Ethers
US9078607B2 (en) 2005-11-01 2015-07-14 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8920319B2 (en) 2005-11-01 2014-12-30 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US8915850B2 (en) 2005-11-01 2014-12-23 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US9326716B2 (en) 2005-11-01 2016-05-03 Abbott Diabetes Care Inc. Analyte monitoring device and methods of use
US20090281406A1 (en) * 2006-06-07 2009-11-12 Abbott Diabetes Care Inc. Analyte Monitoring System and Method
US7920907B2 (en) 2006-06-07 2011-04-05 Abbott Diabetes Care Inc. Analyte monitoring system and method
US20080058625A1 (en) * 2006-06-07 2008-03-06 Abbott Diabetes Care, Inc. Analyte monitoring system and method
US9028859B2 (en) 2006-07-07 2015-05-12 Advanced Cardiovascular Systems, Inc. Phase-separated block copolymer coatings for implantable medical devices
US20080008739A1 (en) * 2006-07-07 2008-01-10 Hossainy Syed F A Phase-separated block copolymer coatings for implantable medical devices
DE112007002581T5 (en) 2006-10-27 2009-12-03 Cms Technology Holdings Inc., Newport Removing water and methanol from fluids
US20120283489A1 (en) * 2006-10-27 2012-11-08 Cms Technologies Holdings Inc. Removal of water from fluids
US7838267B1 (en) 2006-10-27 2010-11-23 Cms Technologies Holdings, Inc. Increasing rate of enzyme catalyzed equilibrium reactions
US20080099400A1 (en) * 2006-10-27 2008-05-01 Cms Technologies Holdings Inc. Removal of Water and Methanol from Fluids
US8506815B2 (en) * 2006-10-27 2013-08-13 Cms Technologies Holdings Inc. Removal of water from fluids
US8293112B2 (en) 2006-10-27 2012-10-23 Cms Technologies Holdings, Inc. Removal of water and methanol from fluids
US9126137B1 (en) 2012-07-18 2015-09-08 Battelle Memorial Institute Polymer nanocomposites for gas separation

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